JPH0350744B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention relates to N-phenyl-N'-alkyl-p
- Polymer-bound catalyst systems for use in the preparation of compounds such as phenylenediamines, and which overcome a number of existing drawbacks in the production of such compounds. The present invention relates to a method for the reductive alkylation of aromatic nitro compounds with ketones. More specifically, the present invention provides N-phenyl-N'-alkyl-p useful as rubber antioxidants and antiozonants.
-This invention relates to an improved synthetic method for phenylene diamines. PRIOR ART Currently, N-phenyl-N'-alkylphenylene diamines are produced by reduction of p-nitrodiphenylamine followed by alkylation. Other methods for producing p-nitrodiphenylamine are described in British Patent Nos. 798148 and 834510;
It is described in German Patent No. 185,663, US Pat. No. 3,155,727 and US Pat. No. 4,155,936. p-Nitrodiphenylamine has the following general formula. In the formula, R and R ₁ are selected from the group consisting of hydrogen and an alkyl group of 1 to 9 carbon atoms, R ₂ and
R ₃ is hydrogen, an alkyl group of 1 to 9 carbon atoms, 1
It is selected from the group consisting of alkoxy groups of 9 to 9 carbon atoms and cycloalkyl groups of 5 to 6 carbon atoms. Currently, p-nitrodiphenylamine is (1) para-halonitrobenzene with the following structural formula: (wherein, X is a halogen selected from the group consisting of chlorine and bromine, and R and R ₁ are as defined above), (2) 1 of the following structural formula
aromatic amine (wherein R ₂ and R ₃ are as defined above); and (3) a neutralization selected from the group consisting of alkali metal salts, oxides of alkali metal salts, and alkali metal hydroxides. (4) in the presence of a catalyst at a concentration of at least 0.1 part by weight per 100 parts by weight of para-halonitrobenzene; under pressure,
(7) It is synthesized by reacting with a 3 to 300 percent excess of primary aromatic amine. The first stage reaction is the production of 4-nitrodiphenylamine. The first stage involves the reduction of 4-nitrodiphenylamine, while the second stage is a reductive alkylation reaction to provide the final product. The current stage commercial reaction involves the reduction of 4-nitrodiphenylamine to 4-nitrodiphenylamine at about 200 DEG C. over a copper chromite catalyst. The second stage is a reaction in which 4-aminodiphenylamine is alkylated with MIBK (methyl isobutyl ketone) at 185°C using a nickel catalyst.
Phenyl-N'-alkyl-p-phenylenediamine is produced. These currently accepted means of synthesis are
It is usually carried out at temperatures below 205°C and for times exceeding 12 hours. Additionally, currently accepted commercial synthetic routes suffer from poor quality in that significant amounts of tars and by-products are present in the final product and require three reaction steps. An improved feature of the present application is the use of a polymer-bonded anthranilic acid-palladium complex and a sulfonic acid-bound resin as catalysts for the first and second stages of the combined reaction. It will be apparent to those skilled in the art that the catalyst systems of the present invention are useful for the preparation of a large number of compounds. No. 4,155,936 is incorporated herein by reference. US Pat. No. 4,155,936 specifically incorporates a solubilizing agent into the reaction mixture to shorten the reaction time of the first stage and improve the yield. Problems to be Solved by the Invention The present invention addresses the problems of long reaction times, limited number of suitable catalysts, environmentally undesirable emissions from the reaction, and multistage reaction. It provides a solution to a problem. The cited patents and literature include N-phenyl-
Concerning unexpected improvements and simplifications in the synthesis of N'-alkyl-p-phenylenediamines,
No hints or disclosures have been made. More specifically, the process of the present invention provides a means to eliminate metal ions in wastewater effluents, improve reaction efficiency, and simplify the process. Means to solve the problem: (1) Using a catalyst system consisting of a polymer-bonded anthranilic acid-Pd complex and (2) a sulfonic acid resin,
The following structural formula is characterized by an improvement in which the reaction is carried out in one step at a temperature of (wherein R and R ₁ are selected from the group consisting of hydrogen and an alkyl group of 1 to 9 carbon atoms, R ₂ and
R ₃ is hydrogen, an alkyl group of 1 to 9 carbon atoms, 1
It is selected from the group consisting of alkoxy groups of 9 to 9 carbon atoms and cycloalkyl groups of 5 to 6 carbon atoms. Disclosed is a method for reductive alkylation of a nitrodiphenylamine compound with a dialkyl ketone. the nitrodiphenylamine compound is p-nitrodiphenylamine, the ketone is MIBK,
The polymer-bound anthranilic acid-palladium complex is
a macroreticular styrene/vinylbenzyl chloride/divinylbenzene resin containing at least 4% crosslinking and 0.001 to 10% by weight palladium, and the sulfonic acid resin is Amberlist 15. A method for doing so is also disclosed. (1) Nitrodiphenylamine with the following structural formula (However, in the above formula, R and R ₁ are selected from the group consisting of hydrogen and an alkyl group of 1 to 9 carbon atoms, and R ₂ and R ₃ are hydrogen, an alkyl group of 1 to 9 carbon atoms, and an alkyl group of 1 to 9 carbon atoms. (2) selected from the group consisting of an alkoxy group of (However, in the previous formula, R, R ₁ , R ₂ and R ₃ are as defined above.) In this case, the reaction is carried out between a polymer-bound anthranilic acid-Pd complex and (2) a polymer-bound sulfone. Also disclosed is a process characterized by an improvement carried out in one step using a catalyst system consisting of an acid resin. The present invention also contemplates a process for the reductive alkylation of a large number of aromatic nitro compounds with either aromatic, aliphatic or aralkyl ketones and aldehydes in one step. It will be understood that the alkyl portion of the ketone useful in this invention does not include any unsaturation. The method of the present invention can be used with or without solubilizing agents such as those disclosed in US Pat. No. 4,155,936. The finishing of the final product is described in US Pat. No. 4,155,936. Representative examples of the ketones of the present invention are as follows. carbonyl compound

[Formula] Acetone

[Formula] Benzyl methyl keto hmm

[Formula] 3-pentanone

[Formula] Benzilp lopil ketone

[Formula] Methyl ethyl ketone

2-Hexanone Those skilled in the art will appreciate that other strongly acidic resins similar to Amberlyst 15 are also suitable for use in the present invention. Amberlyst 15 is a macroreticular, strongly acidic resin known to be useful as a heterogeneous acid catalyst for a wide range of organic reactions in non-aqueous media, particularly non-polar media. For more detailed information, please contact Rohm and Haas.
and Haas Co.) published in May 1972.
Technical Bulletin；lysAAmber15，Synthetic
Please refer to Resin Catalyst. Additionally, the present invention contemplates the use of resins or polymers containing both strong acidic functional groups and metal complex catalysts. Those skilled in the art will appreciate that reaction temperature and pressure conditions will vary depending on the raw materials used, but that 20-200°C and atmospheric pressure to 35,000 kPa are convenient for carrying out the process of the invention. . The preferred temperature range is
60-150℃, pressure 350-7000kPa (50-
1000psi). Those skilled in the art will understand that the catalyst system of the present invention is used in catalytic amounts, which amount depends on the number of mmoles of functional group per gram of resin or polymer. Generally, 0.1 to 1000 mmol of palladium bound to the polymer per mole of nitro compound and 1.0 to 1000 mmol of acid bound to the resin per mole of nitro compound are preferred ratios in the present invention. EXAMPLES The following examples are illustrative and do not limit the scope of the invention. Experiment 1 Representative method for preparing macroreticular styrene/vinylbenzyl chloride/divinylbenzene resin. A 1-liter three-necked flask was equipped with a Teflon stir bar, thermometer sheath, and nitrogen inlet and heated with a Glas-Col mantle. A flask was filled with 300 ml of water and 6.0 g of cellulose 7M (medium viscosity grade from Hercules Rubber Co.). The mixture was stirred vigorously under nitrogen for 10 min, then toluene 150
A solution of 82.16 g (0.7 mole) of styrene, 20.07 g (0.1316 mole) of vinylbenzyl chloride, and 80.5 g (0.395 mole) of 50% pure divinylbenzene was added. Stirring was continued for 10 minutes, then heating was started and azobis-isobutyronitrile 1.5
g (0.0091 mol) was added. Temperature 3-3.5
It was gradually raised to 70-75° over time and maintained there for 4 hours. At the end of the polymerization, the suspension was poured into excess cold water, washed and dried in a hood for 3 days. The final product weight of the resin was 118.3 grams and the nominal (feed) composition was 60/10/30 styrene/vinylbenzyl chloride/divinylbenzene. 50.0 g of this crude resin was washed with acetone followed by perdrying to yield 47.33 g of product. When this washed resin was subjected to elemental analysis, the following results were obtained. Chlorine: Calculated value 2.30%, measured value 1.79%. 2 Preparation of polymer-bound macroreticular anthranilic acid
25.0 g (~0.0164 mol chlorine) of the cleaning resin (60/10/30) prepared above in a 500 ml three-necked flask,
Anthranilic acid 5.0g (0.0365mol), pyridine
5.77 g (0.073 mol) and 250 ml of dimethylformamide (DMF) were charged. The mixture was warmed under nitrogen at 75° C. with stirring for 18 hours. The mixture was then filtered warm and diluted with DMF three times.
Washed three times with acetone, then dried in a vacuum drying oven at 80°C.
After drying for 3 hours, 25.48 g of product resin was obtained. The nitrogen analysis value of the resin was 0.67%. 3 Preparation of palladium, anthranilic acid complex bound to macroreticular polymer Equipped with stirrer, thermometer and condenser
In a 500 ml three-necked flask, 24.8 g (0.012 mol) of the above anthranilic acid resin and 0.89 g of PdCl ₂
(0.005 mol) and 250 ml of DMF were charged. The mixture was stirred and warmed to 75°C under nitrogen for 18 hours. Next, the resin was kept warm and DMF
2 times with DMF/H ₂ O (5/1) and 3 times with acetone and then dried in a vacuum oven to obtain 25.14 g of orange resin. The results of the analysis were 0.65% N and 1.71% Pd. 4 Activation of macroreticular palladium anthranilate complex In a 500 ml three-necked flask equipped with a magnetic stirrer and a nitrogen inlet, add the palladium resin from 3 above.
24.05 g (0.00386 mol Pd) and 200 ml of tetrahydrofuran were charged. After purging with nitrogen,
30ml of 0.5M NaBH ₄ diglyme solution
(0.015 mol) was added via syringe (all at once). The resin rapidly turned black and some gas evolved. After stirring for 30 min at room temperature, filter the product.
Washed twice with THF, three times with ethanol, and twice with toluene, then stored under toluene in a clear bottle for further use. Use of Prepared Catalyst 5 Reduction of p-Nitrodiphenylamine: Low Pressure Experiment 21.4 g (0.10 mol) of p-nitrodiphenylamine recrystallized in a 500 ml Parr hydrogenation bottle, 180 ml of ethanol and 3.0 g of the catalyst from 4 above. g
filled with. After evacuation and repressurization to 350 KPa with hydrogen, heating and shaking were started. Temperature rises up to 74℃, hydrogen absorption occurs within 1 hour
Stopped at 0.3 mol. 18.04 g of pure p-aminodiphenylamine was isolated from the liquid. The catalyst was washed with MIBK and recycled to the next experiment. In the next experiment, use MIBK (180ml) instead of ethanol.
It was used. In this experiment, the reduction was also completed within 1 hour. No Schiff base formation or ketone reduction was observed. 6 N-Phenyl- using the catalyst of 4 above and Amberlyst 15 sulfonic acid resin (trade name of Rohm and Haas, macroreticular sulfonic acid resin containing 4.5 mil equivalents of acid per gram of resin)
Preparation of N'-alkyl-p-phenylenediamine The specific reaction is as follows. The reaction within this one flask is animated by three separate processes. (1) Due to the catalytic action of Pd ⁺² polymer catalyst, p-
A reaction in which nitrodiphenylamine is reduced to p-aminodiphenylamine. (2) A reaction in which the Schiff base of () is formed by MIBK under the catalytic action of a polymeric acidic catalyst (Amberlyst 15). (3) A reaction in which Schiff base () is reduced by the catalytic action of a Pd ⁺² polymer catalyst. A 500 ml hydrogen bottle was charged with 21.4 g (0.10 mol) of recrystallized p-nitrodiphenylamine, 200 ml of methyl isobutyl ketone, 3.0 g of Pd ²⁺ polymer catalyst of 4, and 3.0 g of Amberlyst 15 acid catalyst.
After repressurizing to 345 kPa (50 psig) with evacuated hydrogen, shaking and heating were started. Nitro compounds were reduced very rapidly. i.e. at 75℃
The time required to absorb 0.3 moles of hydrogen was less than 1 hour. After this, the Schiff base was gradually reduced. That is, 0.1 mole of hydrogen was absorbed in 5 hours at 70°C. After cooling and venting, the catalyst was recirculated three more times with similar results. The analytical results of the four experiments are summarized in the table.

[Table] 7 N-phenyl using palladium anthranilate ^{+ 2} polymeric catalyst and Amberlyst 15
Preparation of N'-alkyl-p-phenylenediamine: High-pressure experiment In a 400 ml Parr autoclave, 21.4 g of recrystallized p-nitrodiphenylamine (0.10
mol), 200 ml of methyl isobutyl ketone, catalyst prepared according to 1 to 4 above (0.66% Pd)
5.0 g and Amberlyst 15 resin 5.0 g were charged. The autoclave was sealed and flushed with nitrogen three times. The system was then heated to 70°C and hydrogen was introduced. Pressure from 6900kPa (1000psig)
reduced to 6500kPa (950psig) then 6900kPa
Refilled and pressurized to (1000 psig). The stirring speed was approximately 3500 rpm. Total reaction time of 7 hours (4 hours at 70℃, 3 hours at 102℃
hours) later, hydrogen was no longer absorbed. The results of gas chromatography analysis were as follows. N-phenyl-N'-alkyl-p-phenylenediamine 79.9% Schiff base 3.6% p-aminodiphenylamine 11.6% The first and second stage reactions are carried out together in a high pressure vessel (6900 kPa, 1000 psig _H2 ) Another experiment was also conducted. In the process of the present invention, the yield was improved using a high pressure reactor over a low pressure reaction. 8

Preparation of [Formula] In a 500 ml Par hydrogenation bottle, 0.10 mol of p-nitrophethol, 200 ml of MIBK, 5.0 g of the activated catalysts 1 to 4 above, Amberlyst
Filled with 5.0 grams of 15 resin. The system was flushed with hydrogen and subsequently pressurized to 350 kPa. Shaking and heating were started. A reductive alkylation reaction occurred and the product was obtained. Results and Discussion The present invention has demonstrated that effective macroreticular catalysts can be synthesized from macroreticular resins prepared by a simple suspension copolymerization method. These resins are easily converted to highly active polymer-bound metal chelate catalysts by conventional organic reaction procedures. Additionally, the catalyst has long-term stability on storage, is non-corrosive, non-pyrophoric, and appears to be relatively unaffected by water or air. The ability to synthesize these macroreticular catalysts and resins allows the unique properties of these catalysts and resins to be synthesized in the present invention over a much broader range of conditions than is possible with gel-type resin catalysts or their homogeneous counterparts. Make available. This behavioral difference is clearly demonstrated in the catalytic hydrogenation of p-nitrodiphenylamine. When this compound was hydrogenated in ethanol over a gel-type Pd ⁺² polymer-bonded catalyst, very little reaction occurred during hydrogenation at 345 kPa (50 psig) at 80-90°C for 5 hours. This result is in sharp contrast to the same reaction performed under similar conditions using a Pd ²⁺ macroreticular polymer-bound catalyst. The present invention provides antiozonant N-phenyl-
A catalyst system for the production of N'-alkyl-p-phenylenediamine is provided. In this catalyst system, the stage (p
- preparation of aminodiphenylamine) and step (p
- Reductive alkylation of aminodiphenylamine with MIBK) can be combined in one step. Such a merger would result in substantial cost savings due to reduced distillation costs and increased yields. Industrial Applicability The present invention combines the stage and stage steps of current methods into one step. The present invention also eliminates the copper chromite and modified nickel catalysts used in current commercial processes. With this new method, very little, if any, of the solvent MIBK is reduced to alcohol. Furthermore, the process of the present invention provides a process that can be easily adapted for the commercial reductive alkylation of aromatic nitro compounds and aldehydes or ketones. Although some exemplary embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention.

Claims (1)

[Claims] 1. The following structural formula (wherein R and R ₁ are selected from the group consisting of hydrogen and an alkyl group of 1 to 9 carbon atoms, R ₂ and
R ₃ is hydrogen, an alkyl group of 1 to 9 carbon atoms, 1
It is selected from the group consisting of alkoxy groups of 9 to 9 carbon atoms and cycloalkyl groups of 5 to 6 carbon atoms. ) in the reductive alkylation method of a nitrodiphenylamine compound with a dialkyl ketone using a catalyst system consisting of (1) a polymer-bonded anthranilic acid-palladium complex and (2) a sulfonic acid resin.
The above method, characterized in that the reaction is carried out in one step at a temperature of -200°C and a pressure of from atmospheric pressure to 35000 kPa. 2. The method according to claim 1, wherein the dialkyl ketone is methyl isobutyl ketone. 3. the nitrodiphenylamine compound is p-nitrodiphenylamine, the dialkyl ketone is methyl isobutyl ketone, and the polymer-bound anthranilic acid-palladium complex contains at least 4% by weight
2. The method of claim 1, wherein the sulfonic acid resin is Amberlyst 15. 4. The method according to claim 1, wherein the reaction is carried out at 60-150°C and a pressure of 350-7000 kPa. 5 Polymer-bound anthranilic acid-palladium complex of 60/10/30 styrene/vinyl benzyl chloride/
Claim 3 which is divinylbenzene resin
The method described in section.